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Journal Name
Jou Pr nl e aa ls oe fd Mo an to et r ai ad lj su s Ct hm ea mr g ii sn ts ry C
DOI: 10.1039/C7TC01597F
ARTICLE
Synthesis
yl)ethane-1,2-dione (3): To
of
1-(4-bromophenyl)-2-(4'-tert-butylbiphenyl-4- (0.2 g, 0.20 m mol) was added under nitrogen atmosphere. The
mixture of 1,2-bis(4- solution was heated at 70 °C for 18 hrs. After the reaction mixture
a
bromophenyl)ethane-1,2-dione (1) (0.73g, 2.0 mmol) and 4-tert- was cooled, the product was washed with water and extracted with
butylphenylboronic acid (2) (0.36 g, 2 mmol), THF (40 mL ) and a DCM. Then the product was purified by column chromatography on
solution of K CO3 (15 mL, 2M) were added. Then the reaction silica gel eluting with DCM and PE. The yellowish powder (0.9 g) was
2
1
mixture was degassed for 5 min and tetrakis(triphenylphosphine) obtained. H NMR (400 MHz, CDCl
3
, 25 °C): δ 7.65 (d, J = 8.0 Hz, 2H),
palladium (0.1 g, 0.1 mmol) was poured under Ar atmosphere. After 7.09-7.14 (m, 22H), 6.97-7.01 (m, 12H).
that, solution was heated under reflux for 18 hrs. The reaction
mixture was cooled, followed by the washing of product in water Synthesis
and extracted with the DCM. Purification of the product was done triphenylvinyl)phenyl)-1H-imidazol-2-yl)-[1,1'-biphenyl]-4-amine
by column chromatography on silica gel eluting with DCM and PE. (2TPETPAI): mixture of 1,2-bis(4-(1,2,2-
of
N,N-diphenyl-4'-(1-phenyl-4,5-bis(4-(1,2,2-
A
1
The yellowish powder (0.55 g) was obtained. H NMR (400 MHz, triphenylvinyl)phenyl)ethane-1,2-dione (0.72 g, 1.0 mmol), 4'-
CDCl , 25ºC): δ 8.00-8.02 (d, J = 8 Hz, 2H), 7.85-7.87 (d, J = 8 Hz, 2H), (diphenylamino)-[1,1'-biphenyl]-4-carbaldehyde (0.35 g, 1.0 mmol),
3
7
.71-7.73 (d, J = 8 Hz, 2H), 7.65-7.67 (d, J = 8 Hz, 2H), 7.56-7.58 (d, J aniline (0.46 g, 5.0 mmol) and ammonium acetate (0.4 g, 5.0 mmol)
=
8 Hz, 2H), 7.49-7.51 (d, J = 8 Hz, 2H), 1.36 (s, 9H).
in acetic acid (30 mL ) was heated at 120 °C for 12 hrs under
nitrogen atmosphere. After the reaction mixture was cooled, the
Synthesis
of
1-(4'-tert-butylbiphenyl-4-yl)-2-(4-(1,2,2- product was dissolved in water and extracted with the DCM. The
triphenylvinyl)phenyl)ethane-1,2-dione (5): To a mixture of 1-(4- product was purified by column chromatography on silica gel
bromophenyl)-2-(4'-tert-butylbiphenyl-4-yl)ethane-1,2-dione (3) eluting with DCM and PE. The yellowish powder (0.75 g) was
1
(
0.42g, 1.0 mmol) and 4,4,5,5-tetramethyl-2-(1,2,2-triphenylvinyl)- obtained. H NMR (400 MHz, CDCl , 25 °C): δ 7.41-7.44 (m, 6H),
3
1
,3,2-dioxaborolane (4) (0.72g, 2 mmol), THF (40 mL ) and a solution 7.23-7.34 (m, 10H), 6.91-7.11 (m, 41H), 6.85 (d, J = 8.0 Hz, 2H), 6.80
1
3
2 3
of K CO (15 mL, 2M) were added. The reaction mixture was (d, J = 8.0 Hz, 2H). C NMR (100 MHz, CDCl3) δ 147.60, 147.40,
degassed for 5 min and tetrakis(triphenylphosphine) palladium (0.2 143.98, 143.93, 143.80, 143.50, 143.40, 143.14, 141.56, 141.02,
g, 0.20 mmol) was poured under Ar atmosphere. The solution was 140.73, 140.41, 131.55, 131.40, 131.38, 131.25, 130.90, 130.43,
then heated for 18 hrs. The reaction mixture was cooled, followed 129.37, 129.28, 129.17, 129.01, 128.45, 127.69, 127.61, 127.58,
by the washing of product in water and extracted with the DCM. 126.56, 126.39, 126.30, 126.11, 124.56, 124.46, 123.78, 123.00. FT-
-1
Purification of the product was done through column IR (KBr): 3038, 1590, 1484, 1271, 727, 685 cm . HRMS (MALDI-
+
chromatography on silica gel eluting with DCM and PE. The TOF), m/z: M , calcd for C85
H
61
N
3
, 1124.444; found, 1124.5153.
1
yellowish powder (0.6 g) was obtained. H NMR (400 MHz, CDCl
3
,
Anal. Calcd. for C85
61 3
H N : C, 90.7, H, 5.46, N, 3.75, found: C, 90.71,
2
7
6
5ºC): δ 7.99-8.01 (d, J = 8 Hz, 2H), 7.69-7.73 (t, J = 16 Hz, 4H), 7.56- H, 5.50, N, 3.78.
.58 (d, J = 8 Hz, 2H), 7.48-7.50 (d, J = 8 Hz, 2H), 7.09-7.16 (m, 11H),
.97-7.02 (m, 6H), 1.36 (s, 9H).
Device Fabrication Method:
Synthesis of 4'-(4-(4'-tert-butylbiphenyl-4-yl)-1-phenyl-5-(4-(1,2,2- The organic layers were deposited consecutively on the precleaned
triphenylvinyl)phenyl)-1H-imidazol-2-yl)-N,N-diphenylbiphenyl-4-
ITO-coated glass substrates in a vacuum chamber with a pressure of
amine (BPTPETPAI): A mixture of 1-(4'-tert-butylbiphenyl-4-yl)-2-(4- 2 × 10−4 Torr. Next the cathode was fabricated with thermal
1,2,2-triphenylvinyl)phenyl)ethane-1,2-dione (5) (0.6 g, 1.0 m mol), evaporation of a 1 nm LiF layer followed by a 150 nm aluminium
'-(diphenylamino)-[1,1'-biphenyl]-4-carbaldehyde (6) (0.35 g, 1.0 layer. The deposition rates of all organic materials and aluminium
(
4
mmol), aniline (0.46 g, 5.0 mmol) and ammonium acetate (0.4 g, 5.0 were 1−2Ås−1, while that of the LiF layer was 0.1 Å s−1. The
mmol) in acetic acid (30 mL ) was heated at 120 C for 12 hrs under electrical characteristics of the devices were measured with a
nitrogen atmosphere. The reaction mixture was cooled, followed by Keithley 2400 source meter. The EL spectra and luminance of the
the washing of product in water and extracted with the DCM. The devices were obtained on
a
PR650 spectrometer. The
product was purified through column chromatography on silica gel characteristics of all the OLED devices were determined in ambient
eluting with DCM and PE. The yellowish powder (0.75 g) was laboratory conditions at room temperature.
1
obtained. H NMR (400 MHz, DMSO, 25ºC): δ 6.92-7.59 (m, 50 Hz),
1
3
1
1
1
1
1
1
1
1
.35 (s, 9H). C NMR (400 MHz, CDCl3) δ 150.61, 150.05, 147.61,
47.41, 146.73, 143.95, 143.88, 143.73, 143.58, 143.41, 143.19, 3. Results and Discussion
42.04, 141.52, 141.03, 140.70, 140.42, 140.10, 138.98, 138.17,
37.27, 134.13, 131.48, 131.37, 131.26, 130.52, 129.28, 129.21,
29.17, 129.01, 128.51, 128.48, 127.65, 127.62, 127.58, 127.54,
26.67, 126.60, 126.54, 126.51, 126.33, 126.12, 125.73, 125.68,
24.46, 123.79, 123.00, 34.55, 31.34. FT-IR (KBr): 3038, 2921, 2857,
484, 1271, 813, 750, 717 cm . HRMS (MALDI-TOF), m/z: M , calcd
, 1002.184; found, 1002.6587. Anal. Calcd. for C75
C, 89.87, H, 5.93, N, 4.2, found: C, 89.76, H, 5.96, N, 4.27.
Synthesis
To expand the class of twisted donor-linker-acceptor type
derivatives to fabricate efficient OLEDs
27-29
, we selected imidazole
as the plane to form a twisted geometrical configuration. Therefore,
based on this, two novel multifunctional derivatives with twisted
conformation were designed with the difference of one TPE unit, a
well-known luminogen. For the synthesis of (4'-(4-(4'-tert-
butylbiphenyl-4-yl)-1-phenyl-5-(4-(1,2,2-triphenylvinyl)phenyl)-1H-
imidazol-2-yl)-N,N-diphenylbiphenyl-4-amine) BPTPETPAI (Scheme.
-1
+
for C75
H
59
N
3
59 3
H N :
Synthesis of 1,2-bis(4-(1,2,2-triphenylvinyl)phenyl)ethane-1,2-
dione (7): To a mixture of 1,2-bis(4-bromophenyl)ethane-1,2-dione
1) (0.73g, 2.0 mmol) and 4,4,5,5-tetramethyl-2-(1,2,2-
triphenylvinyl)-1,3,2-dioxaborolane (4) (1.523g, 4 mmol), THF (40
mL ) and a solution of K CO (30 mL, 2M) were added. The mixture
1
), the important intermediates were 1-(4-bromophenyl)-2-(4'-tert-
butylbiphenyl-4-yl)ethane-1,2-dione (3) and 1-(4'-tert-
(
butylbiphenyl-4-yl)-2-(4-(1,2,2-triphenylvinyl)phenyl)ethane-1,2-
dione (5), which were synthesized by Suzuki couplings of 1,2-bis(4-
bromophenyl)ethane-1,2-dione (1) with 4-tert-butylphenylboronic
2
3
was degassed for 5 min and tetrakis(triphenylphosphine) palladium
acid
(2)
and
1-(4-bromophenyl)-2-(4'-tert-butylbiphenyl-4-
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